DFT calculations (PBE1PBE/6-31G(d,p), Def2-TZVPPD) were performed to study the intramolecular C–H amination of an unsaturated carbamate catalyzed by [Pd(LL)(OAc)2] (2), where LL is the bis(sulfoxide) ligand PhS(O)(CH2)2S(O)Ph. The coordination takes place by an associative path over a trigonal-bipyramidal transition state. The LL ligand undergoes a coordination shift from κ2S,S to κ1S, leaving an open position for binding of the substrate (C═C). In the next step, the C–H activation, the transition state for the hydrogen abstraction from the substrate to form the σ-allyl complex has an energy of 124.0 kJ mol–1, which is the highest energy in the whole mechanism (TOF-determining transition state). The σ-allyl converts easily in the π-allyl, the acetic acid molecule leaving the coordination sphere. The remaining acetate receives the second hydrogen from the NH group, while the newly formed acetic acid molecule is replaced by the pendant arm of the LL ligand, and the cyclization takes place (nucleophilic atta...